ORGANOMETALLIC CHEMISTRY
The student must demonstrate a good knowledge of basic organic chemistry and the chemistry of coordination.
The examination includes a final written test of typically 3 h duration. The written test will be organized in the formulation of two questions concerning general topics discussed in the course and of two synthesis exercises related to these topics. The final grade will take into account the accuracy and quality of the responses, the synthetic capacity of the candidate in presenting the required topics
The course aims to provide an in-depth understanding of the synthesis and reactivity of various types of metal-carbon bond. The first part will consist in “synthesis and reactivity” of the most used organometallic compounds of the main-group (with reference only to compounds that have only simple carbon-metal bond) to pass then to study the organometallics of transition (compounds that include both simple bonds and carbon multiple bonds metal). The last part of the course is directed to various methodologies that allow the formation of C-X bonds (X = C, N, O, S, P) using various metals as catalysts of transition and as reactive the various organometallics of main-group studied in the first part of the course.
Metals chemistry of main groups - 1 CFU (4 hours): Introduction to organometallic and synthesis and reactivity of "main group" compounds such as organo-lithium and organo-sodium. Preparation, structure and use in the synthesis of organo-magnesium, organo-zinc and organo-mercury compounds. Overview of the synthesis and reactivity and structures of organo-boron, organo-aluminum, organo-silicon and organo-tin compounds.
Chemistry of organometallic compounds of the transition d - 3 CFU transition (22 hours): Oxidative addition reactions, reductive elimination and migration-insertion, with particular attention to the stereochemistry of the same. Synthesis and reactivity of metal hydrides and metal alkyls. Introduction to the study of metal olefins. Reactions of metal olefins. Synthesis and reactivity of metal alkynes and related reactions such as Pauson-Khand, hetero Pauson-Khand and cyclotrimerization reactions. Introduction to the chemistry of metal carbenes and reactions of various types of metal carbenes. Synthesis, structures, properties and use of carbonyl metals. Synthesis and reactivity of p allylic complexes. Studies on carbonylation and decarbonylation reactions.
Cross coupling reactions - 3 CFU (22 hours): Historical background and Negishi-Kumada reactions, Suzuki and Stille reaction, Hiyama and Sonogashira reactions. Heck reactions and new protocols. C-Cl binding activation and new ligands, C sp3 activation and “T shaped” intermediates, C-F bond activation, types of “heterocoupling” reactions, direct functionalization of C-H bonds.
The course uses lectures. The duration of the same will be 48 hours, will involve the use of a video projector with which will then projected and discussed slides concerning the different topics of the course, slides also contained, for approach to the subject, in three files in advance provided to the students.
Every day at the teacher's office, by appointment made by e-mail at least on the day before that of the desired reception.